Methods for preparing ethers, ether compositions, fluoroether fire extinguishing systems, mixtures and methods

ABSTRACT

Highly fluorinated, saturated, and unsaturated fluoroethers are efficient, economical, non-ozone-depleting fire extinguishing agents used alone or in blends with other fire extinguishing agents in total flooding and portable systems. Methods for producing ethers, halogenated ether intermediates, and fluoroethers are disclosed. Novel fluoroether compositions are disclosed. Fluoroether extinguishing mixtures, methods, and systems are disclosed.

RELATED PATENT DATA

[0001] This patent is a continuation-in-part of internationalapplication PCT/US01/44256, filed Nov. 14, 2001, entitled “FireExtinguishing Methods Utilizing Hydrofluoroethers,” which claimspriority to U.S. provisional patent application 60/249,684, filed Nov.17, 2000, having the same title; this patent also claims priority toU.S. provisional patent application 60/390,202, filed Jun. 20, 2002,entitled “Ethers and Materials and Methods for Producing and Using theSame.”

TECHNICAL FIELD

[0002] The present invention is directed to novel ether compounds and inparticular aspects halogenated ether compounds and in other embodimentsfluorinated ether compounds. Other aspects of the present invention arealso directed to the production of these ether compounds and their uses.

[0003] Certain aspects of the present invention are directed tohydrofluoroether fire extinguishing agents and methods for extinguishingfires using the hydrofluoroethers. Aspects of the present invention aredirected to fire extinguishing agents and methods using saturated orunsaturated, fluorinated C₄ and/or C₅ hydrofluoroethers, and blends ofone or more of the hydrofluoroethers with one or more other fireextinguishing agents.

BACKGROUND OF THE INVENTION

[0004] The use of certain bromine, chlorine, and iodine containinghalogenated chemical agents for the extinguishment of fires is common.These agents are in general thought to be effective due to theirinterference with the normal chain reactions responsible for flamepropagation. The most widely accepted mechanism for flame suppression isthe radical trap mechanism proposed by Fryburg in Review of LiteraturePertinent to Fire Extinguishing Agents and to Basic Mechanisms Involvedin Their Action, NACA-TN 2102 (1950). The finding that the effectivenessof the halogens are on a molar basis in the order Cl<Br<I supports theradical trap mechanism, as reported by Malcom I Vaporizing FireExtinguishing Agents, Report 117, Dept. of Army Engineering Research andDevelopment Laboratories, Fort Bevoir, Va., 1950 (Project-8-76-04-003).It is thus generally accepted that compounds containing the halogens Cl,Br and I act by interfering with free radical or ionic species in theflame and that the effectiveness of these halogens is in the orderI>Br>Cl. In addition, it is generally thought that to be effective as afire extinguishing agent, a compound must contain Cl, Br or I.

[0005] The use of iodine-containing compounds as fire extinguishingagents has been avoided primarily due to the expense of theirmanufacture or due to toxicity considerations. Until very recently, thethree fire extinguishing agents presently in common use were allbromine-containing compounds; Halon 1301 (CF₃Br), Halon 1211 (CF₂BrCl)and Halon 2402 (BrCF₂CF₂Br). The effectiveness of these three volatilebromine-containing compounds in extinguishing fires has been describedin U.S. Pat. No. 4,014,799 to Owens. Certain chlorine containingcompounds are also known to be effective extinguishing agents, forexample Halon 251 (CF₃CF₂Cl) as described by Larsen in U.S. Pat. No.3,844,354.

[0006] Although the above-named bromine or chlorine-containing Halonsare effective fire fighting agents, those agents containing bromine orchlorine are asserted by some to be capable of the destruction of theearth's protective ozone layer. Also, because the agents contain nohydrogen atoms which would permit their destruction in the troposphere,the agents may also contribute to the greenhouse warming effect.

[0007] More recently, hydrofluorocarbons have been proposed for firesuppression, for example in U.S. Pat. No. 5,124,053. However, adisadvantage of these compounds is their relatively high global warmingpotential.

[0008] Recently, ethers, particularly fluoroethers, have been identifiedas compounds that may be useful as halon replacements. Typically, thesecompounds are synthesized with all of the necessary fluorine content inplace.

[0009] It is therefore an object of this invention to provide a methodfor extinguishing fires that extinguishes fires as rapidly andeffectively as the techniques employing Halon agents while avoiding theabove-named drawbacks.

[0010] It is a further object of this invention to provide an agent forthe use in a method of the character described that is efficient,economical to manufacture, and environmentally safe with regard to ozonedepletion and greenhouse warming effects.

[0011] It is a still further object of this invention to provide blendsof the new agents and other fire extinguishing agents that are effectiveand environmentally safe.

SUMMARY OF THE INVENTION

[0012] One embodiment of the present invention provides processes forproducing ethers from olefins and alcohols. In one aspect, the presentinvention provides processes for producing ethers from olefins andmethanol. In a particular aspect, the present invention provides acontinuous process of producing ethers by combining olefins and alcoholsin the presence of an aqueous solution containing a base.

[0013] Another aspect of the present invention provides processes forthe production of halogenated ether intermediates useful in theproduction of fluoroethers. In one aspect, the halogenated etherintermediate can be produced by combining the ether with a halogenatingagent in the presence of ultraviolet (uv) radiation.

[0014] In a further aspect of the present invention, halogenated etherintermediates can be converted to fluoroethers. In one aspect,CF₃CHFCF₂OCCl₃ can be fluorinated in the presence of gaseous HF and acatalyst to produce CF₃CHFCF₂OCF₃. In one aspect, CF₃CHFCF₂OCHF₂ can beproduced by reacting CF₃CHFCF₂OCHCl₂ with HF in the presence of acatalyst.

[0015] In another aspect, the halogenated ether intermediate can befluorinated in the presence of liquid hydrogen fluoride (HF) to obtainthe fluoroether intermediate which can subsequently be fluorinated toform a fluoroether. In an exemplary aspect, CF₃CHFCF₂OCCl₃ can befluorinated in the presence of liquid HF to form CF₃CHFCF₂OCCl₂F whichcan subsequently be fluorinated in the presence of gaseous HF to formCF₃CHFCF₂OCF₃.

[0016] The hydrofluoroethers of this invention may be produced vianumerous routes. For example, CF₃CHFCF₂OCF₂H may be prepared via a threestep process comprising:

[0017] i. reaction of methanol with commercially availablehexafluoropropene (CF₃CF═CF₂) in the presence of base to produceCF₃CHFCF₂OCH₃;

[0018] ii. chlorination of CF₃CHFCF₂OCH₃ with Cl₂ to produceCF₃CHFCF₂OCHCl₂; and

[0019] iii. fluorination of CF₃CHFCF₂OCHCl₂ with HF to produce the finalproduct CF₃CHFCF₂OCF₂H.

[0020] By further reacting with a strong base like sodium or potassiumhydroxide the corresponding unsaturated C₄ or C₅ hydrofluoroethers maybe prepared.

[0021] In still another embodiment of the present invention, ethers ofthe present invention are used as extinguishants (including streamingand total flooding agents), solvents, refrigerants, blowing agents,etchants, anesthetics, and propellants. Novel compositions of mattersuch as CF₃CHFCF₂OCF₃ are also provided.

[0022] The foregoing and other objects, advantages and features of thepresent invention may be achieved by employing saturated or unsaturated,higher fluorinated hydrofluoroethers and blends thereof with otheragents as fire extinguishants for use in fire extinguishing methods andapparatus. More particularly, the method of this invention involvesintroducing to a fire a saturated or unsaturated, fluorinated C₄ or C₅hydrofluoroether in a fire extinguishing concentration and maintainingsuch concentration until the fire is extinguished. Specific saturated,fluorinated C₄ or C₅ hydrofluoroethers of this invention include:CF₃CHFCF₂OCH₃, CF₃CHFCF₂OCH₂F, CF₃CHFCF₂OCF₂H, CF₃CHFCF₂OCF₃,(CF₃)₂CHCF₂OCH₃, (CF₃)₂CHCF₂OCH₂F, (CF₃)₂CHCF₂OCHF₂, and(CF₃)₂CHCF₂OCF₃.

[0023] Specific unsaturated, fluorinated C₄ or C₅ hydrofluoroethers ofthe present invention include: CF₃CF═CFOCH₃, CF₃CF═CFOCH₂F,CF₃CF═CFOCHF₂, CF₃CF═CFOCF₃, CF₂═CFCF₂OCH₃, CF₂═CFCF₂OCH₂F,CF₂═CFCF₂OCF₂H, CF₂═CFCF₂OCF₃, (CF₃)₂C═CFOCH₃, (CF₃)₂C═CFOCH₂F,(CF₃)₂C═CFOCF₂H, (CF₃)₂C═CFOCF₃, CF₂═C(CF₃)CF₂OCH₃, CF₂═C(CF₃)CF₂OCH₂F,CF₂═C(CF₃)CF₂OCF₂H, and CF₂═C(CF₃)CF₂OCF₃.

[0024] These hydrofluoroethers may be used alone, in admixture with eachother or as blends with other fire extinguishing agents. Generally, theagents of this invention are employed at concentrations lying in therange from about 3 to about 15%, preferably from about 5 to about 10% inair, on a v/v basis. The agents of this invention are suitable for usein both total flooding and portable fire suppression applications.Suitable extinguishing agents (“blends”) for admixture with thehydrofluoroethers include CF₃CHFCF₃, CF₃CF₂CF₂H, CF₃CH₂CF₃, CF₃CF₂H, andCF₃H.

[0025] The above and other embodiments, aspects, alternatives, andadvantages of the present invention will become more apparent from thefollowing detailed description of the present invention taken inconjunction with the drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

[0026]FIG. 1. is a diagram of one embodiment of ether production inaccordance with an aspect of the present invention.

[0027]FIG. 2 is an illustration of an application of extinguishingmixtures in accordance with an aspect of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0028] This disclosure of the invention is submitted in furtherance ofthe constitutional purposes of the U.S. Patent Laws “to promote theprogress of science and useful arts” (Article 1, Section 8).

[0029] According to an embodiment of the present invention fluoroethersare produced and utilized to extinguish combustion. For purposes of thisdisclosure the term fluoroethers includes all compounds having an ethergroup and a fluorine atom. Examples of these compounds include, but arenot limited to perfluoroethers, hydrofluoroethers, fluorohalogenatedethers, and/or hydrofluorohalogenated ethers. Exemplary aspects of thepresent invention are described with reference to FIGS. 1 and 2.

[0030] Referring now to FIG. 1, a reaction apparatus 10 including asource of olefin 1, a source of alcohol 2, and basic aqueous solution 4(with the olefin, alcohol, and basic aqueous solution being reagents 7)is shown. The apparatus further includes a reaction vessel 3. In oneaspect, olefin 1, alcohol 2, and a basic aqueous solution 4 are combinedto form an ether containing reaction product 5. Reagents can be combinedin a batch, semi-continuous, or continuous fashion. Reaction product 5can remain in reaction vessel 3 and/or be transferred to a separationvessel 6, as shown, where a crude ether product 8 is separated fromreagents 7. Reagents 7 can then be returned to reaction vessel 3 toreact in the presence of additional or remaining basic aqueous solution4.

[0031] Depending on the specific olefins and alcohols selected asstarting materials, the ether containing reaction product may be removedfrom reaction vessel 3 in a number of forms including as a gas or as atop, middle or bottom liquid layer. Likewise, the separation of crudeether 8 from reagents 7 may involve removal of crude ether product 8 asa gas or as a top, middle, or bottom liquid layer and otherwise removalof reagents 7 as a gas or a top, middle, or bottom layer. Consequently,the return of reagents 7 to reaction vessel 3 may take the form of thereturn of a gas and/or liquid composition.

[0032] Olefin 1 can have the general formula R¹(R²)C═CXY. Olefin 1 cangenerally be referred to as a hydrogenated, halogenated, and/or aperhalogented olefin. R¹ can include lone halogens, lone hydrogens,halogenated alkyl groups, hydrogenated alkyl groups or perhalogenatedalkyl groups either alone or in combination. For purposes of thisdisclosure, the halogenated alkyl groups includes all alkyl groupshaving at least one halogen, regardless of what the remaining elementsof the alkyl might be. For example, and by way of example only,halogenated alkyl groups include but are not limited to —CHFCl, —CF₃, or—CF₂Cl. R² can include lone halogens, lone hydrogens, halogenated alkylgroups, hydrogenated alkyl groups or perhalogenated alkyl groups eitheralone or in combination. R¹ and R² can be the same or different groups.In one aspect R¹ includes CF₃— or F. In one aspect of the presentinvention, R² can be H or F. In one combination, R¹ can be F and R² canbe F. In another combination, R¹ can be F and R² can be H.

[0033] For purposes of this disclosure, X and Y can generally representhydrogen and/or the halogens I, Br, Cl, and/or F. In one aspect of thepresent invention, X and Y can be the same element, for example, X canbe F and Y can be F. In an exemplary aspect, X and Y can be differentelements, for example, X can be F and Y can be H.

[0034] According to an aspect of the present invention, olefin 1includes CF₃CF═CF₂ (hexafluoropropene, HFP), CF₃CH═CF₂(pentafluoropropene, PFP), or CF₂═CF₂ (tetrafluoroethene, TFE). Incertain aspects of the present invention, olefin 1, can comprise,consist, and/or consist essentially of CF₃CF═CF₂. In exemplary aspects,olefin 1 can comprise, consist, and/or consist essentially of CF₂═CF₂.

[0035] Alcohol 2 includes hydrogenated and halogenated alcohols.According to an aspect of the present invention, alcohol 2 can includemethanol (CH₃OH), ethanol (CH₃CH₂OH), and/or isopropanol ((CH₃)₂CHOH).

[0036] Basic aqueous solution 4 can include sufficient base to ensurethe formation of an alkoxide upon combination with an alcohol. Basesthat can be used to form the alkoxide include those of sodium andpotassium such as sodium hydroxide (NaOH) or potassium hydroxide (KOH).In an aspect of the present invention, basic aqueous solution includesKOH.

[0037] According to an aspect of the present invention, basic aqueoussolution 4 includes an aqueous solution having a KOH concentration of10-45% (wt./wt.). This KOH solution can be combined with alcohol 2 inreaction vessel 3 to form a first reactant mixture having an alcoholconcentration of 50-60% (wt./wt.) and a KOH concentration of 5-20%(wt./wt.). Olefin 1 can then be combined with the first reactant mixturein reaction vessel 3. Reaction vessel 3 can have a temperature fromabout −10° C. to about 50° C.

[0038] According to one aspect, the bottom organic phase containingcrude ether 8 can be separated from the top mixture that can includereagents 7. In an exemplary aspect reagents 7 can be returned toreaction vessel 3.

[0039] The crude ether 8 of the present invention can generally bereferred to as an ether or halogenated ether and have the generalformula R³CXY—O—R⁴. The R³ group can include hydrogenated alkyl groups,halogenated alkyl groups, and/or perhalogenated alkyl groups. Forexample, and by way of example only, R³ can include CF₃CHF—, CF₃CH₂—,and/or CHF₂—. The R⁴ group can include hydrogenated alkyl groups,halogenated alkyl groups, and/or perhalogenated alkyl groups. Forexample, and by way of example only, R⁴can include —CH₃, —CH₂CH₃, and/or—CH(CH₃)₂. In an aspect of the present invention, the halogenated etherincludes CF₃CHFCF₂OCH₃. In another aspect of the present invention, thehalogenated ether includes CF₃CH₂CF₂OCH₃. In still another aspect of thepresent invention, the halogenated ether includes CHF₂CF₂OCH₃.Non-limiting examples 1-3 demonstrate aspects of ether preparationaccording to the present invention.

[0040] According to another aspect of the present invention ahalogenated ether intermediate can be formed by reacting an ether with ahalogen in the presence of actinic energy. This reaction can be carriedout in a photochemical reactor. The reactor may be configured to provideactinic energy to its content from an internal and/or an externalsource. For example, and by way of example only, a medium pressuremercury lamp (100 watt, 11.49 watt total radiant energy) can be utilizedto provide the necessary radiation from within the reactor. Otherconfigurations may include the use of 90% 3500 angstrom range of photonblack light providing 24 watts of total radiant energy. The reactor maybe cooled, for example, from a municipal water source.

[0041] The halogen can include chlorine (Cl₂). Depending on the productdesired, halogens such as bromine or iodine may be utilized as well. Thereaction can be performed at a temperature from about 10° C. to about70° C.

[0042] In an exemplary aspect, methods include providing a photochemicalreactor containing an ether. The ether can have the general formulaR³CXY—O—R⁴, as described above.

[0043] The halogenated either intermediate can have the general formulaR⁵CXY—O—R⁶. The R⁵ group can include hydrogenated alkyl groups,halogenated alkyl groups, and/or perhalogenated alkyl groups. Forexample, and by way of example only, R⁵ can include CF₃CHF—, CF₃CClF—,CF₃CH₂—, CF₃CHCl—, CF₃CCl₂—, CHF₂—, and/or CClF₂—. The R⁶ group caninclude halogenated alkyl groups or perhalogenated alkyl groups. Forexample, and by way of example only, R⁶ can include —CH₂Cl, —CHCl₂,and/or —CCl₃. In an aspect of the present invention, the halogenatedether intermediate can include CF₃CHFCF₂OCCl₃. In another aspect of thepresent invention, the halogenated ether intermediate can includeCF₃CHFCF₂OCHCl₂. In still another aspect of the present invention, thehalogenated ether intermediate can include CF₃CHFCF₂OCH₂Cl. In anexemplary aspect, the halogenated ether intermediate can includeCF₃CClFCF₂OCCl₃.

[0044] In certain aspects of the present invention, two halogenatedether intermediates useful in the production of fluoroethers can beproduced according to the present invention. In one aspect, the etherCF₃CHFCF₂OCH₃ can be chlorinated according to the present invention toproduce a mixture of halogenated ether intermediates such asCF₃CHFCF₂OCHCl₂ and CF₃CHFCF₂OCCl₃. Non-limiting Example 4 demonstratesan aspect of the halogenated ether intermediate production methodsaccording to the present invention.

[0045] Another aspect of the present invention provides methods forconverting halogenated ether intermediates to useful fluoroethers.Aspects of the present invention provide efficient processes forfluorinating halogenated ethers to produce heretofore unknown compounds.

[0046] In an aspect of the present invention, the halogenated etherintermediate can have the general formula R⁵CXY—O—R⁶, as describedabove. In an aspect of the present invention, the halogenated etherintermediate can be selectively fluorinated in the presence of HF and acatalyst to produce a fluoroether.

[0047] The catalyst can include a chromium/carbon catalyst that has beenpre-fluorinated. The catalyst utilized may take pure or supported forms.Supports include but are not limited to those of activated carbon. Thecatalysts themselves include but are not limited to such catalysts asthose of chromium, nickel, iron, vanadium, manganese, cobalt, and/orzinc. The preparation can occur from about 100° C. to about 300° C. Incertain aspects, the temperature of the reaction is about 200° C.

[0048] The fluoroether produced can have the general formula R⁷—O—R⁸.The R⁷ group can include hydrogenated alkyl groups,hydrofluorohalogenated alkyl groups, hydrofluorinated alkyl groups,fluorohalogenated alkyl groups, and/or perfluorinated alkyl groups. Forexample, and by way of example only, R⁷ can include CF₃CHFCF₂—,CF₃CClFCF₂—, CF₃CF₂CF₂—, CF₃CH₂CF₂—, CF₃CHClCF₂—, CF₃CCl₂CF₂—, CHF₂CF₂—,CF₃CF₂—, and/or CClF₂CF₂—. The R⁸ group can includehydrofluorohalogenated alkyl groups, hydrofluorinated alkyl groups,fluorohalogenated alkyl groups, and/or perfluorinated alkyl groups. Forexample, and by way of example only, R⁸ can include —CFCl₂, —CF₂Cl,—CF₃, —CHFCl, —CF₂H, and/or CFH₂. In an aspect of the present invention,the fluoroether includes the hydrofluoroether CF₃CHFCF₂OCF₃. In anotheraspect of the present invention, the fluoroether includes thehydrofluoroether CF₃CHFCF₂OCHF₂. In still another aspect of the presentinvention, the fluoroether includes the perfluorinated etherCF₃CF₂CF₂OCF₃.

[0049] According to one aspect of the present invention, an ether can befluorinated in the presence of liquid hydrogen fluoride (HF). In oneaspect, an ether having at least one of the halogens I, Br, or Cl can befluorinated in the presence of liquid HF to produce a fluoroether. Thefluoroether produced according to this aspect of the present inventioncan be characterized as having at least one more fluorine atom than theether. For example, and by way of example only, the ether CF₃CHFCF₂OCCl₃can be fluorinated in the presence of liquid HF to produce thefluoroether CF₃CHFCF₂OCFCl₂. In one aspect of the present invention,this fluorination can occur from about 40° C. to about 120° C. In oneaspect of the present invention, this fluorination can occur atapproximately 70° C.

[0050] The fluoroether produced according to this aspect of the presentinvention may be utilized as starting materials for other aspects of thepresent invention. Accordingly, the ether can be fluorinated at about70° C. and subsequently fluorinated at about 200° C. The ether may alsobe fluorinated at about 70° C. and subsequently fluorinated at about230° C. or 280° C. For example, and by way of example only, the etherCF₃CHFCF₂OCCl₃ can be fluorinated in the presence of liquid HF toproduce the fluoroether CF₃CHFCF₂OCFCl₂, which can be fluorinated in thepresence of HF and a catalyst as described above to produce thehydrofluoroether CF₃CHFCF₂OCF₃.

[0051] An embodiment of the present invention also provides multi-stepsynthetic processes for the production of fluoroethers. According to oneaspect of the present invention, methods are provided for manufacturingfluoroethers that include combining an alcohol with an olefin to producean ether. Subsequently, reacting the ether with a halogenating agent toproduce a halogenated ether intermediate and then fluorinating thehalogenated ether intermediate with HF to from a fluoroether. In anotheraspect, the halogenated ether intermediate can be fluorinated with HF ata first temperature to from a fluoroether intermediate. The fluoroetherintermediate can then be fluorinated with HF at a second temperature toform a fluoroether.

[0052] An embodiment of the present invention also provides halogenatedether compounds. Generally, these ether compounds have the formulaR⁹OR¹⁰. Generally, R⁹ can be partially or fully halogenated, saturatedor unsaturated, organic groups, and R¹⁰ can be partially or fullyhalogenated, saturated or unsaturated organic groups. In particularaspects, these halogenated ether compounds include CF₃CHFCF₂OCF₃. Thestructure of CF₃CHFCF₂OCF₃ was confirmed by gas chromatography massspectrometry (GC-MS) and fluorine (¹⁹F), proton (¹H), and carbon (¹³C)nuclear magnetic resonance (NMR). The boiling point of this compound wasalso determined.

[0053] GC-MS (m/e): 69 (CF₃), 82 (CF₃CH), 101 (CF₃CHF),

[0054] 129 (CHFCF₂OCF or CHCF₂OCF₂), 135 (CF₂OCF₃),

[0055] 151 (CF₃CHFCF₂), 217 (CF₃CHFCF₂OCF₂)

[0056] High Resolution MS Theoretical: 235.98837

[0057] Found: 235.98726

[0058] NMR: F¹⁹ (282 MHz, CFCl₃): δ−55.4 (t,3F, J=8.9 Hz), −75.3 (m,3F), −81.4 (m, 2F), −211.5 (d, t, q, 1F, J=43.64, 10.91 Hz) ppm

[0059] H¹: (300 MHz, CDCl₃): δ4.86 (d, t, q, 1H, J=43.8, 5.51, 5.98 Hz)ppm

[0060] C¹³: (75 MHz, CDCl₃): δ77 (t, J=31.78 Hz), 84.1 (d, t, q,J=204.69, 35.79, 35.79 Hz), 119.2 (q, J=267.68 Hz), 112-125 (m) ppm

[0061] Boiling point: 23-24° C.

[0062] Non-limiting Examples 5, 6, 7, and 8 demonstrate preparationsaccording to aspects of the present invention.

[0063] The present invention also provides fire extinguishing mixtureswhich comprise fluoroether extinguishing agents that can extinguishfires through inertion, and/or dilution, as well as, chemical, physical,and/or thermal extinguishment methods. Thermal extinguishment includes“cooling” a combustion. The present invention also provides methods ofextinguishing, preventing, and/or suppressing a fire using such fireextinguishing mixtures. The present invention further provides fireextinguishing, preventing, and/or suppressing systems for deliveringsuch fire extinguishing mixtures. Exemplary aspects of the presentinvention are described with-reference to FIG. 2.

[0064] Referring to FIG. 2, a space 27 configured with a fireextinguishing system 11 is shown. Fire extinguishing system 11 includesan extinguishing agent storage vessel 13 contiguous with anextinguishing agent dispersing nozzle 17. As depicted, a combustion 21occurs within a pan 23 on a pedestal 25. An extinguishing mixture 19exists within space 27 and is applied to combustion 21 to substantiallyextinguish the flame.

[0065] While depicted in two dimensions, space 27, for purposes of thisdisclosure, should be considered to have a volume determined from itsdimensions (e.g., width, height and length). While FIG. 2 illustrates asystem configured for extinguishing fires within a space that, asillustrated, appears to be enclosed, the application of the mixtures,systems, and methods of the present invention are not so limited. Insome aspects, the present invention may be used to extinguish fires inopen spaces, as well as, confined spaces.

[0066] All combustion suitable for extinguishment, suppression orprevention using the mixtures of the present invention or utilizing themethods and systems according to the present invention, are at leastpartially surrounded by a space. The available volume of this space canbe filled with the compositions of the present invention to extinguish,suppress, and/or prevent combustion. Typically, the available volume isthat volume which can be occupied by a liquid or a gas [i.e. that volumewithin which fluids (gases and liquids) can exchange]. Solidconstructions typically are not part of the available volume.

[0067] Furthermore, FIG. 2 illustrates a single extinguishing agentstorage vessel 13. It should be understood that extinguishing mixture 19can be provided to room 27 from multiple extinguishing agent storagevessels 13 and the present invention should not be limited to mixtures,methods, and/or systems that can be provided from a single vessel normethods or systems that utilize a single vessel. Generally, combustion21 is extinguished when extinguishing mixture 19 is introduced fromvessel 13 through nozzle 17 to space 27. It should also be understood,that while FIG. 2 illustrates a single nozzle 17, multiple nozzles maybe utilized, and the present invention should not be limited tomixtures, methods, and/or systems utilizing a single nozzle.

[0068] In one aspect of the present invention, extinguishing mixture 19can comprise, consist essentially of, and/or consist of a fluoroetherextinguishing agent. In another aspect, extinguishing mixture 19 cancomprise, consist essentially of, and/or consist of a fluoroetherextinguishing agent and a suppressing additive and/or other fireextinguishing agents.

[0069] The suppressing additive employed can include diluent gases,water, and/or mixtures thereof. Exemplary diluent gases can includenitrogen, argon, helium, carbon dioxide, and/or mixtures thereof. In anexemplary aspect, these gases can deprive fires of necessaryingredients, such as oxygen and/or fuel. In the same or other aspects,these diluent gases resist decomposition when exposed to combustion. Insome cases, these gases are referred to as inert gases. An exemplarydiluent gas can comprise, consist essentially of, and/or consist ofnitrogen.

[0070] In accordance with the present invention, the saturated andunsaturated C₄ and C₅ hydrofluoroethers of the present invention havebeen found to be effective fire extinguishants at concentrations safefor use.

[0071] Specific hydrofluoroethers useful in accordance with thisinvention are: CF₃CHFCF₂OCH₃, CF₃CHFCF₂OCH₂F, CF₃CHFCF₂OCF₂H,CF₃CHFCF₂OCF₃, (CF₃)₂CHCF₂OCH₃, (CF₃)₂CHCF₂OCH₂F, (CF₃)₂ ₂OCHF₂,(CF₃)₂CHCF₂OCF₃, CF₃CF═CFOCH₃, CF₃CF═CFOCH₂F, CF₃CF═CFOCHF₂,CF₃CF═CFOCF₃, CF₂═CFCF₂OCH₃, CF₂═CFCF₂OCH₂F, CF₂═CFCF₂OCF₂H,CF₂═CFCF₂OCF₃, (CF₃)₂C═CFOCH₃, (CF₃)₂C═CFOCH₂F, (CF₃)₂C═CFOCF₂H,(CF₃)₂C═CFOCH₃, CF₂═C(CF₃)CF₂OCH₃, CF₂═C(CF₃)CF₂OCH₂F,CF₂═C(CF₃)CF₂OCF₂H, and CF₂═C(CF₃)CF₂OCF₃.

[0072] Generally, these ether compounds have the formula R⁹OR¹⁰.Generally, R⁹ can be partially or fully halogenated, saturated orunsaturated, organic groups, and R¹⁰ can be partially or fullyhalogenated, saturated or unsaturated organic groups. More specificallythe extinguishing compounds of the present invention can have thegeneral formula Z¹-O-Z². The Z¹ group can include CF₃CHFCF₂—,CF₃CF₂CF₂—, (CF₃)₂CHCF₂—, CHF₂CF₂—, CF₂═C(CF₃)—, CF₃CF═CF—, CF₂═CFCF₂—,CF₃CH═CF—, CF₃CHBrCF₂—, CF₃CFBrCF₂— or CF₂BrCF₂—. The Z² group caninclude —CHF₂, —CF₃, —CH₂F, —CH₂Br, —CFBr₂, —CHFBr or —CF₂Br. Inparticular aspects the extinguishing compound includes CF₃CHFCF₂OCF₃and/or CF₃CHFCF₂OCHF₂.

[0073] These hydrofluoroethers may be used alone, as admixtures witheach other or as blends with other fire extinguishing agents. Generally,when a single hydrofluoroether of this invention is employed,concentrations lying in the range from about 3 to about 15%, preferablyfrom about 5 to about 10% in air, on a v/v basis, are used; whenemployed as admixtures, concentrations lying in the range from about 3to about 15%, preferably from about 5 to about 10% in air, on a v/vbasis, are used. Where the hydrofluoroethers of this invention areemployed in admixture with other fire extinguishing agents (“blends”),the hydrofluoroethers desirably comprise of at least about 10% by weightof the blends, and the overall concentration of the blend lies in therange from about 3 to about 15%, preferably from about 5 to about 10% inair, on a v/v basis. The agents of this invention are suitable for usein both total flooding and portable fire suppression applications.Suitable extinguishing agents for blends with the hydrofluoroethersinclude CF₃CHFCF₃, CF₃CF₂CF₂H, CF₃CH₂CF₃, CF₃CHFCF₂H, CF₃CF₂H, and CF₃H.

[0074] It should be understood that the % (v/v) values set forth in thisdescription and in the claims are based on space volume and refer to thedesign concentration as adopted and described by the National FireProtection Association in NFPA 2001, Standard on Clean Agent FireExtinguishing, 2000 edition.

[0075] The equation used to calculate the concentrations ofextinguishing compounds has likewise been adopted by the National FireProtection Association and is as follows:

W=V/s(C/100−C)

[0076] Where:

[0077] W=weight of extinguishing compound (kg)

[0078] V=volume of test space (m³)

[0079] s=specific volume of extinguishing compound at test temperature(m³/kg)

[0080] C=concentration (% (v/v))

[0081] The novel ethers according to the present invention may be usedin conjunction with difluoromethane (HFC-32), chlorodifluoromethane(HCFC-22), 2,2-dichloro-1,1,1-trifluoroethane (HCFC-123),1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a),2-chloro-1,1,1,2-tetrafluoroethane(HCFC-124),1-chloro-1,1,2,2-tetrafluoroethane (HCFC-124a),pentafluoroethane (HFC-125), 1,1,2,2-tetrafluoroethane (HFC-134),1,1,1,2-tetrafluoroethane (HFC-134a),3,3-dichloro-1,1,1,2,2-pentafluoropropane (HCFC-225ca),1,3-dichloro-1,1,2,2,3-pentafluoropropane (HCFC-225cb),2,2-dichloro-1,1,1,3,3-pentafluoropropane (HCFC-225aa),2,3-dichloro-1,1,1,3,3-pentafluoropropane (HCFC-225da),1,1,1,2,2,3,3-heptafluoropropane(HFC-227ca),1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea),1,1,1,2,3,3-hexafluoropropane (HFC-236ea), 1,1,1,3,3,3-hexafluoropropane(HFC-236fa), 1,1,1,2,2,3-hexafluoropropane (HFC-236cb),1,1,2,2,3,3-hexafluoropropane (HFC-236ca),3-chloro-1,1,2,2,3-pentafluoropropane (HCFC-235ca),3-chloro-1,1,1,2,2-pentafluoropropane (HCFC-235cb),1-chloro-1,1,2,2,3-pentafluoropropane (HCFC-235cc),3-chloro-1,1,1,3,3-pentafluoropropane (HCFC-235fa),1,1,1,3,3-pentafluoropropane (HFC-245fa),3-chloro-1,1,1,2,2,3-hexafluoropropane (HCFC-226ca),1-chloro-1,1,2,2,3,3-hexafluoropropane (HCFC-226cb),2-chloro-1,1,1,3,3,3-hexafluoropropane (HCFC-226da),3-chloro-1,1,1,2,3,3-hexafluoropropane (HCFC-226ea),2-chloro-1,1,1,2,3,3-hexafluoropropane (HCFC-226ba), and inert gasessuch as nitrogen.

[0082] The C₄ or C₅ hydrofluoroethers of this invention may beeffectively employed at substantially any minimum concentrations atwhich fire may be extinguished, the exact minimum level being dependenton the particular combustible material, the particular hydrofluoroether,and the combustion conditions. In general, however, acceptable resultsare achieved where the hydrofluoroethers or mixtures and blends thereofare employed at a level of at least about 3% (v/v). Wherehydrofluoroethers alone are employed, acceptable results are achievedwith agent levels of at least about 5% (v/v). Likewise, the maximumamount to be employed will be governed by matters of economics andpotential toxicity to living things. About 15% (v/v) provides aconvenient maximum concentration for use of hydrofluoroethers andmixtures and blends thereof in occupied areas. Concentrations above 15%(v/v) may be employed in unoccupied areas, with the exact level beingdetermined by the particular combustible material, the hydrofluoroether(or mixture or blend thereof) chosen, and the conditions of combustion.A concentration of the hydrofluoroether agents, mixtures, and blends inaccordance with an aspect of this invention lies in the range of about 5to 10% (v/v).

[0083] In particular aspects, an extinguishing mixture comprising,consisting essentially of, and/or consisting of CF₃CHFCF₂OCF₃ may beemployed. CF₃CHFCF₂OCF₃ can be employed at concentrations of about 5%(v/v).

[0084] Hydrofluoroethers may be applied using conventional applicationtechniques and methods used for Halons such as Halon 1301 and Halon1211. Thus, these agents may be used in a total flooding fireextinguishing system in which the agent is introduced to an enclosedregion (e.g., a room or other enclosure) surrounding a fire at aconcentration sufficient to extinguish the fire. In accordance with thepresent invention, a total flooding system apparatus, equipment, or evenrooms or enclosures may be provided with a source of agent andappropriate piping, valves, and controls so as to automatically and/ormanually introduce an appropriate concentration in the event that fireshould break out. Thus, as is known to those skilled in the art, thefire extinguishant may be pressurized with nitrogen or other inert gasat up to about 600 psig at ambient conditions.

[0085] Alternatively, the hydrofluoroether agents may be applied to afire through the use of conventional portable fire extinguishingequipment. It is usual to increase the pressure in portable fireextinguishers with nitrogen or other inert gases in order to insure thatthe agent is completely expelled from the extinguisher. Hydrofluoroethercontaining systems in accordance with this invention may be convenientlypressurized at any desirable pressure up to about 600 psig at ambientconditions.

[0086] The compounds of the present invention are nondestructive agents,and are especially useful where cleanup of other media poses a problem.Some of the applications of the hydrofluoroethers of this invention arethe extinguishing of liquid and gaseous fueled fires, the protection ofelectrical equipment, ordinary combustibles such as wood, paper, andtextiles, hazardous solids, and the protection of computer facilities,data processing equipment, and control rooms.

[0087] One aspect of the present invention is based on the finding thatan effective amount of a composition consisting essentially of the novelether according to the present invention will prevent and/or extinguishfire based on the combustion of combustible materials, particularly inan enclosed space, without adversely affecting the atmosphere from thestandpoint of toxicity to humans, ozone depletion, or “greenhouseeffect.”

[0088] It has been determined that the use of the novel ethers,according to the present invention would comprise a habitableatmosphere, which does not sustain combustion of combustible materialsof the non-self-sustaining type. Non-self-sustaining combustiblematerials include materials which do not contain an oxidizer componentcapable of supporting combustion.

[0089] The novel ethers according to the present invention can also beintroduced to a fire for suppression purposes as a liquid or gas orcombination of both. This is sometimes referred to as utilizing thecomposition as a streaming agent. The novel ethers according to thepresent invention can be introduced to fires in combination with othercompounds as blends.

[0090] In another aspect, the invention provides a process forpreventing and controlling fire in an enclosed air-containingmammalian-habitable compartment which contains combustible materials ofthe non-self-containing type which comprises (a) introducing the novelether of the present invention into the air in the enclosed compartmentin an amount sufficient to suppress combustion of the combustiblematerials in the enclosed compartment; and/or (b) introducing oxygen inan amount from zero to the amount required to provide, together with theoxygen present in the air, sufficient total oxygen to sustain mammalianlife.

[0091] In still another embodiment of the present invention, ethers ofthe present invention are used either alone or as blends asextinguishants, including streaming and total flooding agents, solvents,refrigerants, blowing or expansion agents, etchants, anesthetics,propellants, and as power cycle working fluids.

[0092] The novel ethers of the present invention may be used to producerefrigeration by condensing the ether either alone or as a blend andthereafter evaporating the condensate in the vicinity of a body to becooled. The novel ether of the present invention may also be used toproduce heat by condensing the refrigerant in the vicinity of the bodyto be heated and thereafter evaporating the refrigerant.

[0093] The invention will be further described with reference to thefollowing specific Examples. However, it will be understood that theseExamples are illustrative in nature and not restrictive in nature. Wherereferenced, G.C. area % corresponds to percentage area of peak incomparison to all peaks generated when the respective sample is analyzedby a gas chromatograph equipped with a flame ionization detector and asilica-plot column.

EXAMPLE 1 Ether Preparation aq. KOH

CF₃CF═CF₂+CH₃OH CF₃CHFCF₂OCH₃

[0094] An aqueous 45% (wt./wt.) KOH solution is added to methanol toproduce a mixture containing 60% (wt./wt.) methanol and 18% (wt./wt.)KOH. This mixture is placed in a three-neck glass flask equipped with adry ice condenser, a dip tube, and a thermometer. HFP is fed through thedip tube into the solution at −3° C. to 0° C. The condenser is kept at−30 to −40° C. in order to condense unreacted HFP back into the reactor.A water bath is used to control the exothermic reaction. When thesolution becomes a milky suspension, the mixture is drawn out of thereactor and allowed to phase separate. The bottom organic phasecontaining crude CF₃CHFCF₂OCH₃ is separated out, and the top mixturewith additional methanol is fed back to the reactor. Four aliquots ofthe crude CF₃CHFCF₂OCH₃ are collected at time intervals and analyzed bygas chromatography for lights, unreacted olefin, ether, and heavies. Theresults are shown below in Table 1. TABLE 1 aq. KOH CF₃CF═CF₂ + CH₃OHCF₃CHFCF₂OCH₃ Crude Product Col- (G.C. Area %) Ali- lected Olefin quot(g) Lights CF₃CF═CF₂ CF₃CHFCF₂OCH₃ Heavies A 22.5 trace 4.04 89.09 6.12B 18.5 0.46 3.49 88.72 6.73 C 26.6 0.44 3.49 85.59 9.73 D 97.84 trace5.14 87.78 6.11

EXAMPLE 2 Ether Preparation aq. KOH

CF₃CF═CF₂+CH₃OH CF₃CHFCF₂OCH₃

[0095] Example 2 is performed as Example 1 with the modification thatthe reaction is performed using an aqueous mixture having 13% (wt./wt.)KOH and 57% (wt./wt.) methanol at 15° C. to 25° C., and two collectionaliquots are taken and analyzed by gas chromatography. The gaschromatography results are reported below in Table 2. TABLE 2 aq. KOHCF₃CF═CF₂ + CH₃OH CF₃CHFCF₂OCH₃ Crude Product Col- G.C. Area % Ali-lected Olefin quot (g) Lights CF₃CF═CF₂ CF₃CHFCF₂OCH₃ Heavies A 77.2trace 0.65 94.99 3.68 B 45 trace 1.69 95.08 2.12

EXAMPLE 3 Ether Preparation aq. KOH

CF₂═CF₂+CH₃OH CHF₂CF₂OCH₃

[0096] Example 3 is performed as example 1 with the modification thatthe reaction is performed in a 600 cc stainless steel pressure reactorusing an aqueous mixture having 10% (wt./wt.) KOH and 50% (wt./wt.)methanol. The reactor is cooled to −10° C. and then pressurized withtetrafluoroethylene (CF₂═CF₂) which is first passed through a bubblerfilled with α-pinene. The reaction is carried out at 60° C. under 60psig to generate 97% (G.C. Area %) pure CHF₂CF₂OCH₃. Nopolytetrafluoroethylene is visually observed.

EXAMPLE 4 Preparation of Halogenated Ether Intermediates uv Light

CF₃CHFCF₂OCH₃+Cl₂ CF₃CHFCF₂OCHCl₂+CF₃CHFCF₂OCCl₃

[0097] This reaction is carried out in a jacketed glass photochemicalreactor cooled with tap water. A medium pressure mercury lamp (100 watt,11.49 watt total radiant energy) is used for the reaction. Chlorine gasis bubbled into 400 g of liquid CF₃CHFCF₂OCH₃ at 20° C.-30° C. andby-product HCl is vented to a water scrubber. The reaction is stopped,the crude reaction mixture is sampled, analyzed by gas chromatography,and then distilled. Two major products are generated in the reaction,CF₃CHFCF₂OCHCl₂ [37% (G.C. Area %), b.p. 75° C. @ 42 cmHg] andCF₃CHFCF₂OCCl₃ [61% (G.C. Area %), b.p. 82° C. @ 32 cmHg] for a total of482 g of recovered crude material.

EXAMPLE 5 Preparation of Fluoroethers Cr/AC—Gas phase

CF₃CHFCF₂OCHCl₂+HF CF₃CHFCF₂OCHF₂

[0098] 50 g chromium/carbon catalyst is charged to a 0.5 inch×24 inchlong Inconel® tubing reactor which is heated using radiant heat. Afterpre-fluorinating the catalyst, HF and 99.8% pure CF₃CHFCF₂OCHCl₂ are fedinto a reactor at predetermined rates and temperature under atmosphericpressure. The crude product is collected in an ice water scrubber andwashed with H₂O, dried over MgSO₄, and purified by distillation. Theboiling point of the resulting CF₃CHFCF₂OCHF₂ is 47-48° C. and thedensity d=1.529. GC analysis of the collections corresponding to theparameters utilized are shown in the Table 3 below. TABLE 3 Cr/AC - gasphase CF₃CHFCF₂OCHCl₂ + HF CF₃CHFCF₂OCHF₂ Contact HF/R_(f)OCHCl₂ timeG.C. Area % Run Temp. (° C.) (mole ratio) (sec) R_(f)OCHF₂ R_(f)OCHFClR_(f)OCHCl₂ 1 120 7.6/1 17 95.6 1.11 0.23 2 125 6.2/1 21 99.2 0.05 0.0033 150 7.8/1 12 98.3 0.23 0.003 4 150 6.0/1 11.6 98.8 0.05 0.927

EXAMPLE 6 Preparation of Fluoroethers Cr₂O₃—Gas Phase

CF₃CHFCF₂OCCl₃+HF CF₃CHFCF₂OCF₃

[0099] 38 g chromium (III) oxide catalyst^(†) is charged to a 0.5inch×14.125 inch long Inconel® tubing reactor which is heated by aceramic fiber heater. The catalyst is dried under nitrogen at 250-300°C. After drying, the catalyst is prefluorinated at 250-300° C. using aHF:N₂ mixture (using a 1:20 dilution). This prefluorination is continueduntil HF is detected exiting the reactor. At this point, the nitrogen isturned off, and the temperature is increased to 350° C. The catalyst isheld under these conditions for 16 hours. After pre-fluorinating thecatalyst, HF and CF₃CHFCF₂OCCl₃ were fed into the reactor atpredetermined rates and temperature under atmospheric pressure. Thecrude product is washed with H₂O, passed over calcium sulfate, andcollected in a dry ice/acetone cooled trap. GC analysis of the reactorproducts corresponding to the parameters utilized are shown in the Table4 below. The boiling point of the resulting CF₃CHFCF₂OCF₃ was 23-24° C.TABLE 4 Cr₂O₃ - gas phase CF₃CHFCF₂OCCl₃ + HF CF₃CHFCF₂OCF₃ ContactHF/R_(f)OCCl₃ time G.C. Area % Run Temp. (° C.) (mole ratio) (sec)R_(f)OCF₃ CF₃CHFCF₃ 1 150 6.04 8.66 4.28 15.78 2 175 7.12 8.13 62.0012.21 3 200 7.12 8.09 71.89 13.67 4 200 10.87 19.27 72.58 15.41 5 20021.07 8.43 77.06 12.01 6 250 8.0 6.58 30.4 52.23

EXAMPLE 7 Preparation of Fluoroethers Liquid Phase

CF₃CHFCF₂OCCl₃+HF CF₃CHFCF₂OCFCl₂

[0100] 405 g of CF₃CHFCF₂OCCl₃ produced according to the presentinvention is placed in a stainless steel pressure reactor. The reactoris cooled to −9° C. and 76 g of HF is added to the reactor. The reactionis carried out at 70° C., and a pressure of 300 psig is maintained inthe reactor by venting the formed HCl to a water scrubber. 367.6 g crudeproduct is collected. Gas chromatography analysis showed 91.1% (G.C.Area %) of CF₃CHFCF₂OCFCl₂, 3.6% (G.C. Area %) of CF₃CHFCF₂OCF₂Cl, and3.5% (G.C. Area %) of unreacted CF₃CHFCF₂OCCl₃.

EXAMPLE 8 Preparation of Fluoroethers Cr/AC—Gas Phase

CF₃CHFCF₂OCFCl₂+HF CF₃CHFCF₂OCF₃

[0101] Similar set-up and procedure was used as in Example 6 above.After pre-fluorinating the catalyst, HF and 99% pure CF₃CHFCF₂OCFCl₂ arefed into a reactor at predetermined rates and temperature underatmospheric pressure. The resulting crude product is passed through aheated scrubber and collected in a trap cooled by dry ice/acetone. Thisliquid is then dried over CaSO₄ and GC analysis of the collected crudemixtures is shown in Table 5. The collected material is combined anddistilled to give two fractions of CF₃CHFCF₂OCF₃ of 99.6% and 99.77%G.C. assay at a boiling point of 23-24° C. TABLE 5 Cr/AC - gas phaseCF₃CHFCF₂OCFCl₂ + HF CF₃CHFCF₂OCF₃ Contact HF/R_(f)OCFCl₂ Time G.C. Area% Run Temp. (° C.) (mole ratio) (sec) HFC-227ea R_(f)OCF₃ R_(f)OCF₂Cl 1230 9.4/1  9 3.7 91.7  2.7 2 200 10/1  11 6.6 66.8 24.4

EXAMPLE 9

[0102] This example demonstrates the desirable “throw” obtainable withthe fire suppression agents of the present invention when employed inportable (“streaming”) applications. The throw is the distance thestream of agent can be discharged; the longer the throw the better, asthis allows extinguishment without approaching the fire at too close adistance, which can lead to exposure of the operator to fire and toxicfumes from the combustion process.

[0103] A 150 mL SS cylinder is equipped with an inlet tube and a diptube connected via an on/off valve to a delivery nozzle. The cylinder ischarged with 50 grams of CF₃CHFCF₂OCF₂H and then pressurized withnitrogen to the desired pressure. The cylinder contents are completelydischarged and the throw distance noted (Table 6). TABLE 6 Throw vs.Pressure for CF₃CHFCF₂OCF₂H System Pressure, psig Throw, feet 25 10 8015 120 17 150 18

EXAMPLE 10

[0104] This example demonstrates the extinguishment of Class B fireswith the agents of the present invention. A 150 mL SS cylinder isequipped with an inlet tube and a dip tube connected via an on/off valveto a delivery nozzle. The cylinder is charged with 30 grams ofCF₃CHFCF₂OCF₂H and then pressurized with nitrogen to 120 psig. A 2inch×4 inch×0.5 inch SS pan is filled with 20 mL of methanol. Themethanol is ignited and allowed to burn for 30 seconds; the agent isthen dischaged from a distance of 4 feet onto the fire. The methanolfire can be extinguished in 1.5 seconds; a total of 16 grams of agentwas discharged.

EXAMPLE 11

[0105] The method of Example 10 is employed with acetone, isopropanol,and heptane fuels. All fires are rapidly extinguished (see Table 7).TABLE 7 Extinguishment with CF₃CHFCF₂OCF₂H Extinguishing Agentdischarged, Fuel Time, seconds Grams Acetone 2.0 25 Isopropanol 1.5 21Heptane 1.8 11

EXAMPLE 12

[0106] This example demonstrates the extinguishment of deep-seated ClassA fires with the agents of the present invention. A 150 mL SS cylinderis equipped with an inlet tube and a dip tube connected via an on/offvalve to a delivery nozzle. The cylinder is charged with 30 grams ofCF₃CHFCF₂OCF₂H and then pressurized with nitrogen to 120 psig. A woodcrib can be constructed of six layers of 6 inch×2 inch by 0.125 inchstrips of kiln dried fir, each layer consisting of 4 pieces. The crib issoaked with heptane, ignited, and allowed to burn for five minutes. Theagent is then discharged onto the fire, rapid (<2 seconds)extinguishment can be achieved; a total of 25 grams of agent isdischarged. Immediately after extinguishment, the wood crib is cold tothe touch, demonstrating the efficient suppression afforded by theagent.

EXAMPLE 13 CF₃CHFCF₂OCF₃ Cup Burner

[0107] Extinguishing concentrations of the hydrofluoroetherCF₃CHFCF₂OCF₃ can be determined using a cup burner apparatus, asdescribed in M. Robin and Thomas F. Rowland, “Development of a StandardCup Burner Apparatus: NFPA and ISO Standard Methods, 1999 Halon OptionsTechnical Working Conference, Apr. 27-29, 1999, Albuquerque, N.Mex.” andincorporated herein by reference. The cup burner method is a standardmethod for determining extinguishing mixtures and has been adopted inboth national and international fire suppression standards. For example,NFPA 2001 Standard on Clean Agent Fire Extinguishing Systems and ISO14520-1: Gaseous Fire-Extinguishing Systems, both utilize the cup burnermethod.

[0108] A mixture of air and CF₃CHFCF₂OCF₃ is flowed through an 85 mm(ID) Pyrex chimney around a 28 mm (OD) fuel cup. A wire mesh screen anda 76 mm (3 inch) layer of 3 mm (OD) glass beads are employed in thediffuser unit to provide thorough mixing of air and CF₃CHFCF₂OCF₃.

[0109] n-Heptane is gravity fed to a cup from a liquid fuel reservoirconsisting of a 250 mL separatory funnel mounted on a laboratory jack,which can allow for an adjustable and constant liquid fuel level in thecup. The fuel is ignited with a propane mini-torch and the chimney isplaced on the apparatus. The fuel level is then adjusted such that fuelis 1-2 mm from the ground inner edge of the cup. A 90 second preburnperiod is allowed, and a primary flow of air is initiated via acalibrated flow meter @ 20-40 L/min.

[0110] Primary and secondary air flows are monitored by calibrated flowmeters (210, 225, 230 and 240 tubes). The flows are maintained until theflames are extinguished. A constant primary flow (240 tube) between 20to 40 L/min is maintained in all the tests. The secondary flow of air ispassed through CF₃CHFCF₂OCF₃ contained in a 1150 ml steel mixing chamberequipped with a dip tube. The secondary flow, containing air saturatedwith CF₃CHFCF₂OCF₃, exits the mixing chamber and is mixed with theprimary air flow before entering the cup burner's diffuser unit.

[0111] Immediately following flame extinction, a sample of the gasstream at a point near the lip of the cup is collected through a lengthof plastic tubing attached to a three way valve and multifit gassyringe. The sample is then subjected to gas chromatographic analysis(G.C.). G.C. calibration is performed by preparing standards samples ina 1L Tedlar® (E.I. DuPont De Nemours and Co. Corp., 1007 Market Street,Wilmington, Del.) bag.

[0112] A summary of test parameters and results are shown below in Table8. TABLE 8 Extinguishment of n-heptane Flames with CF₃CHFCF₂OCF₃ PrimaryAirflow CF₃CHFCF₂OCF₃ Test (L/min) % (v/v) 1 20.6 4.97 2 20.6 5.40 320.6 5.38 4 20.6 5.38 5 34.2 4.90 6 41.1 5.18 7 41.1 5.13 8 41.1 5.37 941.1 5.40 10  41.1 5.36

[0113] Additional objects, advantages, and other novel features of theinvention will become apparent to those skilled in the art uponexamination of the foregoing or may be learned with practice of theinvention. The foregoing description of the embodiments of the inventionhas been presented for purposes of illustration and description. It isnot intended to be exhaustive or to limit the invention to the preciseform disclosed. Obvious modifications or variations are possible in thelight of the above teachings. Embodiments were chosen and described toprovide the best illustrations of the principals of the invention andtheir practical application, thereby enabling one of ordinary skill inthe art to utilize the invention in various embodiments and with variousmodifications as are suited to the particular use contemplated. All suchmodifications and variations are within the scope of the invention asdetermined by the appended claims when interpreted in accordance withthe breadth to which they are fairly, legally, and equitably entitled.

The invention claimed is:
 1. A method for extinguishing a firecomprising the steps of introducing to the fire a fire extinguishingconcentration of a composition comprising a compound selected from thegroup consisting of CF₃CHFCF₂OCH₂F, CF₃CHFCF₂OCF₂H, CF₃CHFCF₂OCF₃,(CF₃)₂CHCF₂OCH₃, (CF₃)₂CHCF₂OCH₂F, (CF₃)₂CHCF₂OCHF₂, (CF₃)₂CHCF₂OCF₃,CF₃CF═CFOCH₃, CF₃CF═CFOCH₂F, CF₃CF═CFOCHF₂, CF₃CF═CFOCF₃, CF₂═CFCF₂OCH₃,CF₂═CFCF₂OCH₂F, CF₂═CFCF₂OCF₂H, CF₂═CFCF₂OCF₃, (CF₃)₂C═CFOCH₃,(CF₃)₂C═CFOCH₂F, (CF₃)₂C═CFOCF₂H, (CF₃)₂C═CFOCH₃, CF₂═C(CF₃)CF₂OCH₃,CF₂═C(CF₃)CF₂OCH₂F, CF₂═C(CF₃)CF₂OCF₂H, and CF₂═C(CF₃)CF₂OCF₃.
 2. Themethod of claim 1, wherein the compound is selected from the groupconsisting of CF₃CHFCF₂OCH₃, CF₃CHFCF₂OCH₂F, CF₃CHFCF₂OCF₂H,CF₃CHFCF₂OCF₃, (CF₃)₂CHCF₂OCH₃, (CF₃)₂CHCF₂OCH₂F, (CF₃)₂CHCF₂OCHF₂,(CF₃)₂CHCF₂OCF₃.
 3. The method of claim 1, wherein the compound isemployed at a level of at least about 3% (v/v).
 4. The method of claim1, wherein the compound is employed in a total flooding system.
 5. Themethod of claim 1, wherein the compound is employed in a portableextinguishing system.
 6. The method of claim 1, wherein the compositioncomprises a blend with other fire extinguishing agents.
 7. The method ofclaim 6, wherein the other fire extinguishing agents are selected fromthe group consisting of CF₃CHFCF₃, CF₃CF₂CF₂H, CF₃CH₂CF₃, CF₃CF₂H, andCF₃H.
 8. A fire extinguishing agent comprising a compound selected fromthe group consisting of CF₃CHFCF₂OCH₂F, CF₃CHFCF₂OCF₂H, CF₃CHFCF₂OCF₃,(CF₃)₂CHCF₂OCH₃, (CF₃)₂CHCF₂OCH₂F, (CF₃)₂CHCF₂OCHF₂, (CF₃)₂CHCF₂OCF₃,CF₃CF═CFOCH₃, CF₃CF═CFOCH₂F, CF₃CF═CFOCHF₂, CF₃CF═CFOCF₃, CF₂═CFCF₂OCH₃,CF₂═CFCF₂OCH₂F, CF₂═CFCF₂OCF₂H, CF₂═CFCF₂OCF₃, (CF₃)₂C═CFOCH₃,(CF₃)₂C═CFOCH₂F, (CF₃)₂C═CFOCF₂H, (CF₃)₂C═CFOCH₃, (CF₃)₂C═CFOCH₂F,(CF₃)₂C═CFOCF₂H, (CF₃)₂C═CFOCH₃, CF₂═C(CF₃)CF₂OCH₃, CF₂═C(CF₃)CF₂OCH₂F,CF₂═C(CF₃)CF₂OCF₂H, and CF₂═C(CF₃)CF₂OCF₃.
 9. A method of makingCF₃CHFCF₂OCF₂H comprising the steps of: reacting methanol withhexafluoropropene in the presence of base to produce CF₃CHFCF₂OCH₃;chlorinating CF₃CHFCF₂OCH₃ with Cl₂ to produce CF₃CHFCF₂OCHCl₂; andfluorinating CF₃CHFCF₂OCHCl₂ with HF to produce CF₃CHFCF₂OCF₂H.
 10. Amethod of making a saturated, fluorinated C₄ or C₅ hydrofluoroethercomprising the steps of: reacting a C1 alcohol with a fluorinated C₃ orC4 alkene in the presence of a base to form a first reaction product;chlorinating the first reaction product with Cl₂ to form a secondreaction product; and fluorinating the second reaction product with HFto form a saturated, fluorinated C₄ or C₅ hydrofluoroether.
 11. Themethod of claim 10, wherein the base is selected from the groupconsisting of sodium and potassium hydroxide.
 12. The compositioncomprising CF₃CHFCF₂OCF₃.
 13. A method for preparing an ethercomprising: mixing a basic aqueous solution with an alcohol to form afirst reactant mixture; providing an olefin having the general formulaR¹(R²)C═CXY, wherein the R¹ group is selected from the group comprisinghydrogens, halogens, halogenated alkyl groups, hydrogenated alkyl groupsor perhalogenated alkyl groups, R² is selected from the group comprisinghydrogens, halogens, halogenated alkyl groups, hydrogenated alkyl groupsor perhalogenated alkyl groups, X and Y are selected from the groupcomprising H, I, Br, Cl, or F, and X and Y can be the same as oneanother or different; and combining the first reactant mixture with theolefin to form an ether having the general formula R³CXY—O—R⁴, whereinthe R³ group is selected from the group comprising hydrogenated alkylgroups, halogenated alkyl groups, or perhalogenated alkyl groups and theR⁴ group is selected from the group comprising hydrogenated alkylgroups, halogenated alkyl groups, or perhalogenated alkyl groups. 14.The method of claim 13, wherein the basic aqueous solution compriseshydroxide.
 15. The method of claim 13, wherein the basic aqueoussolution comprises KOH.
 16. The method of claim 15, wherein the basicaqueous solution comprises from about 10% (wt./wt.) to about 45%(wt./wt.) KOH.
 17. The method of claim 13, wherein the alcohol comprisesmethanol.
 18. The method of claim 13, wherein the first reactant mixturecomprises from about 50% (wt./wt.) to about 60% (wt./wt.) alcohol. 19.The method of claim 13, wherein the R¹ group is selected from the groupcomprising CF₃— or F.
 20. The method of claim 13, wherein the R² groupis selected from the group comprising H or F.
 21. The method of claim13, wherein the R¹ group comprises CF₃— and the R² group comprises F.22. The method of claim 13, wherein the R¹ group comprises F and the R²group comprises F.
 23. The method of claim 13, wherein the R¹ groupcomprises F and the R² group comprises H.
 24. The method of claim 13,wherein the X is the same element as the Y.
 25. The method of claim 13,wherein the X comprises F and the Y comprises F.
 26. The method of claim13, wherein the X comprises F and the Y comprises H.
 27. The method ofclaim 13, wherein the X comprises H and the Y comprises H.
 28. Themethod of claim 13, wherein the olefin is selected from the groupcomprising CF₃CF═CF₂, CF₃CH═CF₂, or CF₂═CF₂.
 29. The method of claim 13,wherein the olefin comprises CF₃CF═CF₂.
 30. The method of claim 13,wherein the olefin consists essentially of CF₃CF═CF₂.
 31. The method ofclaim 13, wherein the olefin consists of CF₃CF═CF₂.
 32. The method ofclaim 13, wherein the olefin comprises CF₂═CF₂.
 33. The method of claim13, wherein the olefin consists essentially of CF₂═CF₂.
 34. The methodof claim 13, wherein the olefin consists of CF₂═CF₂.
 35. The method ofclaim 13, wherein the combining is performed in a reaction vessel havinga temperature from about −10° C. to about 50° C.
 36. The method of claim13, wherein the R³ group is selected from the group comprising CF₃CHF—,CF₃CH₂—, or CHF₂—.
 37. The method of claim 13, wherein the R³ groupcomprises CF₃CHF—.
 38. The method of claim 13, wherein the R³ groupcomprises CHF₂—.
 39. The method of claim 13, wherein the R⁴ group isselected from the group comprising —CH₃, —CH₂CH₃ or —CH(CH₃)₂.
 40. Themethod of claim 13, wherein the R⁴ group comprises —CH₃.
 41. The methodof claim 13, wherein the ether comprises CF₃CHFCF₂OCH₃.
 42. The methodof claim 13, wherein the ether comprises CHF₂CF₂OCH₃.
 43. The method ofclaim 13, wherein the ether comprises CF₃CH₂CF₂OCH₃.
 44. The method ofclaim 13, further comprising separating the ether from the olefin andalcohol by removing the ether in liquid form.
 45. The method of claim13, wherein the preparation of the ether further includes the formationof at least two layers, a bottom layer comprising the ether and an upperlayer comprising an aqueous solution.
 46. The method of claim 45,wherein the first reactant mixture comprises the upper layer.
 47. Amethod for preparing halogenated ether intermediates comprising:providing a photochemical reactor containing an ether having the generalformula R³CXY—O—R⁴, wherein the R³ group is selected from the groupcomprising hydrogenated alkyl groups, halogenated alkyl groups, orperhalogenated alkyl groups and the R⁴ group is selected from the groupcomprising hydrogenated alkyl groups, halogenated alkyl groups, orperhalogenated alkyl groups, X and Y are selected from the groupcomprising H, I, Br, Cl, or F, and X and Y can be the same as oneanother or different; and reacting the ether with a gaseous halogenatingagent in the presence of actinic energy to produce a halogenated etherintermediate having the general formula R⁵CXY—O—R⁶, wherein the R⁵ groupis selected from the group comprising halogenated alkyl groups, orperhalogenated alkyl groups and the R⁶ group is selected from the groupcomprising halogenated alkyl groups, or perhalogenated alkyl groups. 48.The method of claim 47, wherein the R³ group is selected from the groupcomprising CF₃CHF—, CF₃CH₂—, or CHF₂—.
 49. The method of claim 47,wherein the R³ group comprises CF₃CHF—.
 50. The method of claim 47,wherein the R³ group comprises CHF₂—.
 51. The method of claim 47,wherein the R⁴ group is selected from the group comprising —CH₃, —CH₂CH₃or —CH(CH₃)₂.
 52. The method of claim 47, wherein the R⁴ group comprises—CH₃.
 53. The method of claim 47, wherein the ether comprisesCF₃CHFCF₂OCH₃.
 54. The method of claim 47, wherein the ether comprisesCHF₂CF₂OCH₃.
 55. The method of claim 47, wherein the ether comprisesCF₃CH₂CF₂OCH₃.
 56. The method of claim 47, wherein the X is the sameelement as the Y.
 57. The method of claim 47, wherein the X comprises Fand the Y comprises F.
 58. The method of claim 47, wherein the Xcomprises F and the Y comprises H.
 59. The method of claim 47, whereinthe X comprises H and the Y comprises H.
 60. The method of claim 47,wherein the actinic energy comprises uv radiation.
 61. The method ofclaim 47, wherein the gaseous halogenating agent comprises chlorine. 62.The method of claim 47, wherein the reacting occurs at a temperaturefrom about 10° C. to about 70° C.
 63. The method of claim 47, whereinthe reacting occurs at about 50° C.
 64. The method of claim 47, whereinthe R⁵ group is selected from the group comprising CF₃CHF—, CF₃CClF—,CF₃CH₂—, CF₃CHCl—, CF₃CCl₂—, CHF₂— or CClF₂—.
 65. The method of claim47, wherein the R⁵ group comprises CF₃CHF—.
 66. The method of claim 47,wherein the R⁵ group comprises CHF₂—.
 67. The method of claim 47,wherein the R⁶ group is selected from the group comprising —CH₂Cl,—CHCl₂, or —CCl₃.
 68. The method of claim 47, wherein the R⁶ groupcomprises —CHCl₂.
 69. The method of claim 47, wherein the R⁶ groupcomprises —CCl₃.
 70. The method of claim 47, wherein the halogenatedether intermediate comprises CF₃CHFCF₂OCCl₃.
 71. The method of claim 47,wherein the halogenated ether intermediate comprises CF₃CHFCF₂OCHCl₂.72. The method of claim 47, wherein the halogenated ether intermediatecomprises CF₃CClFCF₂OCCl₃.
 73. The method of claim 47, wherein thehalogenated ether intermediate comprises CF₃CHFCF₂OCH₂Cl.
 74. The methodof claim 47, wherein the halogenated ether intermediate comprisesCClF₂CF₂OCCl₃.
 75. The method of claim 47, wherein the halogenated etherintermediate comprises CF₃CH₂CF₂OCCl₃.
 76. A method for preparingfluoroethers comprising: providing a halogenated ether intermediatecomprising R⁵CXY—O—R⁶, wherein the R⁵ group is selected from the groupcomprising hydrogenated alkyl groups, halogenated alkyl groups, orperhalogenated alkyl groups and the R⁶ group is selected from the groupcomprising halogenated alkyl groups or perhalogenated alkyl groups, Xand Y are selected from the group comprising H, I, Br, Cl, or F, and Xand Y can be the same as one another or different, wherein thehalogenated ether intermediate includes at least one halogen selectedfrom the group comprising I, Br, or Cl; fluorinating the halogenatedether intermediate in the presence of HF and a catalyst to produce afluoroether comprising R⁷—O—R⁸, wherein the R⁷ group is selected fromthe group comprising hydrogenated alkyl groups, hydrofluorohalogenatedalkyl groups, hydrofluorinated alkyl groups, fluorohalogenated alkylgroups, or perfluorinated alkyl groups and R⁸ is selected from the groupcomprising hydrofluorohalogenated alkyl groups, hydrofluorinated alkylgroups, fluorohalogenated alkyl groups, or perfluorinated alkyl groups.77. The method of claim 76, wherein the R⁵ group is selected from thegroup comprising CF₃CHF—, CF₃CClF—, CF₃CH₂—, CF₃CHCl—, CF₃CCl₂—, CHF₂—,or CClF₂—.
 78. The method of claim 76, wherein the R⁵ group comprisesCF₃CHF—.
 79. The method of claim 76, wherein the R⁵ group comprisesCHF₂—.
 80. The method of claim 76, wherein the R⁶ group is selected fromthe group comprising —CH₂Cl, —CHCl₂, or —CCl₃.
 81. The method of claim76, wherein the R6 group comprises —CHCl₂.
 82. The method of claim 76,wherein the R⁶ group comprises —CCl³.
 83. The method of claim 76,wherein the halogenated ether intermediate comprises CF₃CHFCF₂OCCl₃. 84.The method of claim 76, wherein the halogenated ether intermediatecomprises CF₃CHFCF₂OCHCl₂.
 85. The method of claim 76, wherein thehalogenated ether intermediate comprises CF₃CHFCF₂OCH₂Cl.
 86. The methodof claim 76, wherein the halogenated ether intermediate comprisesCF₃CClFCF₂OCCl₃.
 87. The method of claim 76, wherein the halogenatedether intermediate comprises CClF₂CF₂OCCl₃.
 88. The method of claim 76,wherein the halogenated ether intermediate comprises CF₃CCl₂CF₂OCCl₃.89. The method of claim 76, wherein the X is the same element as the Y.90. The method of claim 76, wherein the X comprises F and the Ycomprises F.
 91. The method of claim 76, wherein the X comprises F andthe Y comprises H.
 92. The method of claim 76, wherein the X comprises Hand the Y comprises H.
 93. The method of claim 76, wherein the HF is ingas form.
 94. The method of claim 76, wherein the fluorination occurs ata temperature of from about 100° C. to about 300° C.
 95. The method ofclaim 76, wherein the fluorination occurs at about 200° C.
 96. Themethod of claim 76, wherein the catalyst comprises chromium.
 97. Themethod of claim 76, wherein the catalyst comprises activated carbon. 98.The method of claim 76, wherein R⁷ is selected from the group comprisingCF₃CHFCF₂—, CF₃CClFCF₂—, CF₃CF₂CF₂—, CF₃CH₂CF₂—, CF₃CHClCF₂—,CF₃CCl₂CF₂—, CHF₂CF₂—, CF₃CF₂—, or CClF₂CF₂—.
 99. The method of claim76, wherein R⁷ comprises CF₃CHFCF₂—.
 100. The method of claim 76,wherein R⁸ is selected from the group comprising —CFCl₂, —CF₂Cl, —CF₃,—CHFCl, —CF₂H, or —CFH₂.
 101. The method of claim 76, wherein thefluoroether comprises CF₃CHFCF₂OCF₃.
 102. The method of claim 76,wherein the fluoroether comprises CF₃CHFCF₂OCHF₂.
 103. The method ofclaim 76, wherein the fluoroether comprises CF₃CF₂CF₂OCF₃.
 104. A methodfor the preparation of fluoroethers comprising: providing an etherhaving at least one halogen selected from the group comprising I, Br, orCl; and fluorinating the ether in the presence of liquid HF at a firsttemperature to produce a first fluoroether having at least one morefluorine atom than the ether.
 105. The method of claim 104 wherein theether comprises the general formula R⁵CXY—O—R⁶, wherein the R⁵ group isselected from the group comprising hydrogenated alkyl groups,halogenated alkyl groups, or perhalogenated alkyl groups and the R⁶group is selected from the group comprising hydrogenated alkyl groups,halogenated alkyl groups, or perhalogenated alkyl groups, X and Y areselected from the group comprising H, I, Br, Cl, or F, and X and Y canbe the same as one another or different, wherein the halogenated etherintermediate includes at least one halogen selected from the groupcomprising I, Br, or Cl.
 106. The method of claim 104, wherein the R⁵group is selected from the group comprising CF₃CHF—, CF₃CClF—, CF₃CH₂—,CF₃CHCl—, CF₃CCl₂—, CHF₂—, or CClF₂—.
 107. The method of claim 104,wherein the R⁵ group comprises CF₃CHF—.
 108. The method of claim 104,wherein the R⁵ group comprises CHF₂—.
 109. The method of claim 104,wherein the R⁶ group is selected from the group comprising —CH₂Cl,—CHCl₂, or —CCl₃.
 110. The method of claim 104, wherein the R⁶ groupcomprises —CHCl₂.
 111. The method of claim 104, wherein the R⁶ groupcomprises —CCl₃.
 112. The method of claim 104, wherein the ethercomprises CF₃CHFCF₂OCCl₃.
 113. The method of claim 104, wherein theether comprises CF₃CHFCF₂OCHCl₂.
 114. The method of claim 104, whereinthe ether comprises CF₃CHFCF₂OCH₂Cl.
 115. The method of claim 104,wherein the ether comprises CF₃CClFCF₂OCCl₃.
 116. The method of claim104, wherein the ether comprises CClF₂CF₂OCCl₃.
 117. The method of claim104, wherein the ether comprises CF₃CH₂CF₂OCCl₃.
 118. The method ofclaim 104, wherein the X is the same element as the Y.
 119. The methodof claim 104, wherein the X comprises F and the Y comprises F.
 120. Themethod of claim 104, wherein the X comprises F and the Y comprises H.121. The method of claim 104, wherein the X comprises H and the Ycomprises H.
 122. The method of claim 104, wherein the first temperatureis from about 40° C. to about 120° C.
 123. The method of claim 104,wherein the first temperature is about 70° C.
 124. The method of claim104, wherein the first fluoroether is selected from the group comprisingCF₃CHFCF₂OCFCl₂, CF₃CHFCF₂OCF₂Cl, CHF₂CF₂OCFCl₂, or CHF₂CF₂OCF₂Cl. 125.The method of claim 104, further comprising fluorinating the firstfluoroether in the presence of HF at a second temperature to produce asecond fluoroether comprising R⁷—O—R⁸, wherein the R⁷ group is selectedfrom the group comprising hydrogenated alkyl groups,hydrofluorohalogenated alkyl groups, hydrofluorinated alkyl groups,fluorohalogenated alkyl groups or perfluorinated alkyl groups and R⁸ isselected from the group comprising hydrofluorohalogenated alkyl groups,hydrofluorinated alkyl groups, fluorohalogenated alkyl groups orperfluorinated alkyl groups.
 126. The method of claim 125 wherein thefirst temperature is lower than the second temperature.
 127. The methodof claim 125, wherein the first temperature is from about 40° C. toabout 120° C. and the second temperature is from about 100° C. to about300° C.
 128. The method of claim 125, wherein the first temperature isabout 70° C. and the second temperature is about 230° C.
 129. The methodof claim 125, wherein the first temperature is about 70° C. and thesecond temperature is about 200° C.
 130. The method of claim 125,wherein the fluorinating of the first fluoroether occurs in the presenceof a catalyst.
 131. The method of claim 130, wherein the catalystcomprises chromium.
 132. The method of claim 130, wherein the catalystcomprises activated carbon.
 133. The method of claim 130, wherein thefluorination or the first fluoroether occurs in the presence of gaseousHF.
 134. The method of claim 125, wherein R⁷ is selected from the groupcomprising CF₃CHFCF₂—, CF₃CClFCF₂—, CF₃CF₂CF₂—, CF₃CH₂CF₂—, CF₃CHClCF₂—.CF₃CCl₂CF₂—, CHF₂CF₂—, CF₃CF₂—, or CClF₂CF₂—.
 135. The method of claim125, wherein R⁷ comprises CF₃CHFCF₂—.
 136. The method of claim 125,wherein R⁸ is selected from the group comprising —CFCl₂, —CF₂Cl, —CF₃,—CHFCl, —CF₂H, or —CFH₂.
 137. The method of claim 125, wherein thesecond fluoroether comprises CF₃CHFCF₂OCF₃.
 138. The method of claim125, wherein the second fluoroether comprises CF₃CHFCF₂OCHF₂.
 139. Themethod of claim 125, wherein the second fluoroether comprisesCF₃CF₂CF₂OCF₃.
 140. The method of claim 125, wherein the secondfluoroether comprises CHF₂CF₂OCF₃.
 141. The method of claim 125, whereinthe second fluoroether comprises CHF₂CF₂OCHF₂.
 142. A method formanufacturing fluoroethers comprising: combining an alcohol with anolefin to produce an ether; reacting the ether with a halogenating agentto produce a halogenated ether intermediate; and fluorinating thehalogenated ether intermediate with HF to form a fluoroether.
 143. Amethod for manufacturing fluoroethers comprising: combining an alcoholwith an olefin to produce an ether; reacting the ether with ahalogenating agent to produce a halogenated ether intermediate; in thefirst instance, fluorinating the halogenated ether intermediate with HFat a first temperature to form a fluoroether intermediate; and in thesecond instance, fluorinating the fluoroether intermediate with HF at asecond temperature to form a fluoroether.
 144. A mixture within a spacecomprising an extinguishing compound having the general formula Z¹-O-Z²,wherein Z¹ is selected from the group comprising CF₃CHFCF₂—, CF₃CF₂CF₂—,(CF₃)₂CHCF₂—, CHF₂CF₂—, CF₂═C(CF₃)—, CF₃CF═CF—, CF₂═CFCF₂—, CF₃CH═CF—,CF₃CHBrCF₂—, CF₃CFBrCF₂—, or CF₂BrCF₂— and Z² is selected from the groupcomprising —CHF₂, —CF₃, —CH₂CF₃, —CH₂Br, —CFBr₂, or —CF₂Br.
 145. Themixture of claim 144, wherein the extinguishing compound comprises about0.1% (v/v) to about 10% (v/v) of the space.
 146. The mixture of claim144, wherein the extinguishing compound comprises CF₃CHFCF₂OCHF₂. 147.The mixture of claim 145, wherein the CF₃CHFCF₂OCHF₂ comprises fromabout 0.1% (v/v) to about 6% (v/v) of the space.
 148. The mixture ofclaim 145, wherein the CF₃CHFCF₂OCHF₂ comprises about 6% (v/v) of thespace.
 149. The mixture of claim 144, wherein the extinguishing compoundconsists essentially of CF₃CHFCF₂OCHF₂.
 150. The mixture of claim 144,wherein the extinguishing compound consists of CF₃CHFCF₂OCHF₂.
 151. Themixture of claim 144, wherein the extinguishing compound comprisesCF₃CHFCF₂OCF₃.
 152. The mixture of claim 151, wherein the CF₃CHFCF₂OCF₃comprises from about 4%(v/v) to about 6% (v/v) of the space.
 153. Themixture of claim 151, wherein the CF₃CHFCF₂OCF₃ comprises about 5% (v/v)of the space.
 154. The mixture of claim 144, wherein the extinguishingcompound consists essentially of CF₃CHFCF₂OCF₃.
 155. The mixture ofclaim 144, wherein the extinguishing compound consists of CF₃CHFCF₂OCF₃.156. A method for one or more of extinguishing, suppressing orpreventing a fire in a space by introducing to the space a mixturecomprising an extinguishing compound having the general formula Z¹-O-Z²,wherein Z¹ is selected from the group comprising CF₃CHFCF₂—, CF₃CF₂CF₂—,(CF₃)₂CHCF₂—, CHF₂CF₂—, CF₂═C(CF₃)—, CF₃CF═CF—, CF₂═CFCF₂—, CF₃CH═CF—,CF₃CHBrCF₂—, CF₃CFBrCF₂—, or CF₂BrCF₂— and Z² is selected from the groupcomprising —CHF₂, —CF₃, —CH₂CF₃, —CH₂Br, —CFBr₂, or —CF₂Br.
 157. Themethod of claim 156, wherein the extinguishing compound comprises about0.1% (v/v) to about 10% (v/v) of the space.
 158. The method of claim156, wherein the extinguishing compound comprises CF₃CHFCF₂OCHF₂. 159.The method of claim 158, wherein the CF₃CHFCF₂OCHF₂ comprises from about0.1% (v/v) to about 6% (v/v) of the space.
 160. The method of claim 158,wherein the CF₃CHFCF₂OCHF₂ comprises about 6% (v/v) of the space. 161.The method of claim 156, wherein the extinguishing compound comprisesCF₃CHFCF₂OCF₃.
 162. The method of claim 161, wherein the CF₃CHFCF₂OCF₃comprises from about 4% (v/v) to about 6% (v/v) of the space.
 163. Themethod of claim 161, wherein the CF₃CHFCF₂OCF₃ comprises about 5% (v/v)of the space.
 164. A fire extinguishing, preventing or suppressingsystem configured to introduce to a space a mixture comprising anextinguishing compound having the general formula Z¹-O-Z², wherein Z¹ isselected from the group comprising CF₃CHFCF₂—, CF₃CF₂CF₂—, (CF₃)₂CHCF₂—,CHF₂CF₂—, CF₂═C(CF₃)—, CF₃CF═—, CF₂═CFCF₂—, CF₃CH═CF—, CF₃CHBrCF₂—,CF₃CFBrCF₂—, or CF₂BrCF₂— and Z² is selected from the group comprising—CHF₂, —CF₃, —CH₂CF₃, —CH₂Br, —CFBr₂, or —CF₂Br.
 165. The system ofclaim 164, wherein the extinguishing compound comprises about 0.1% (v/v)to about 10% (v/v) of the space.
 166. The system of claim 164, whereinthe extinguishing compound comprises CF₃CHFCF₂OCHF₂.
 167. The system ofclaim 166 wherein the CF₃CHFCF₂OCHF₂ comprises from about 0.1% (v/v) toabout 6% (v/v) of the space.
 168. The system of claim 166 wherein theCF₃CHFCF₂OCHF₂ comprises about 6% (v/v) of the space.
 169. The system ofclaim 164 wherein the extinguishing compound comprises CF₃CHFCF₂OCF₃.170. The system of claim 169, wherein the CF₃CHFCF₂OCF₃ comprises fromabout 4% (v/v) to about 6% (v/v) of the space.
 171. The system of claim169, wherein the CF₃CHFCF₂OCF₃ comprises about 5% (v/v) of the space.